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In this Letter, we describe a simple, practical approach in which cheap CuI was used as a catalyst to introduce a gem-difluoro olefin onto simple electron-rich aniline derivatives in good yield via direct C-H functionalization and a subsequent HF elimination reaction. Detailed mechanistic studies point at a dual role of aniline derivatives in this reaction, which serve as a substrate and a basic promoter to trigger the HF elimination step.We report a heterometallic seed-mediated synthesis method for monodisperse penta-twinned Cu nanorods